Metal phthalocyanine dyestuffs containing a dihaloisothiazole carboxamido group



United States Patent 3,480,641 METAL PHTHALOCYANINE DYESTUFFS CON-TAINING A DIHALOISOTHIAZOLE CARBOX- AMIDO GROUP Karl-HeinzSchiindehiitte, Opladen, and Kersten Trautner, Cologne-Stammheim,Germany (both Farbenfabriken Bayer AG., Leverkusen, Germany) No Drawing.Original application July 6, 1965, Ser. No. 469,907. Divided and thisapplication Dec. 29, 1965, Ser. No. 517,424 Claims priority,appilclation Germany, July 17, 1964,

Int. Cl. C07f 107/00; Dll6p 3/24; C07d 91/34 US. Cl. 260--299 3 ClaimsABSTRACT OF THE DISCLOSURE Dyestuffs of the formula wherein F is aradical of an organic dyestuff, W is a bridge member, X and Y arehalogen atoms, arylthio or aryloxy, and m is an integer. The dyestuffsof this invention are particularly suitable for dyeing textile materialscontaining nitrogen or hydroxyl groups, i.e., cellulose, Wool, silk,synthetic polyamide, and polyurethane.

This application is a division of copending application Ser. No.469,907, filed July 6, 1965, now abandoned.

The present invention relates to new valuable dyestuffs of the generalformula is linked with the dyestuff molecule via any bridge member. TheNH group is of special interest as a bridge member. However, thecarboxyl group can also be linked to, for example, a secondary aminogroup or an amide group, e.g. a sulphonamide or carbonamide,aminotriazine or aminodiazine group. The amino group can, in turn, belinked to the basic dyestuff molecule, i.e. to an aromatic nucleus ofthe dyestuff molecule, directly or via an alkylene, aralkylene, orarylene group. If the bridge members W contain heterocyclic ringsystems, such as triazinylamino and pyrimidinylamino radicals, these mayalso contain reactive halogen atoms.

3,480,641 Patented Nov. 25, 1969 'ice The preferred bridge member, W,may be represented by the following group:

wherein the N atom is connected with the CO grouping of the isothiazolylradical; R is lower alkyl or lower alkyl substituted by OH; and n is 0or 1.

The preferred reactive substituents X and Y in the isothiazole radicalare halogens, such as chlorine and bromine.

Dependent upon the type of their substituents, the new dyestuffs of theFormula I can be water-soluble as well as barely soluble or insoluble inwater. The radical F may contain the substituents customary for thedyestuffs concerned, such as sulphonic acid, carboxylic acid, possiblysubstituted sulphonamide, sulphone, alkylaminoaralkylamino, arylamino,acylamino, nitro, cyano, halogen, hydroxyl, alkoxy, thioether, azogroupings and the like. The dyestuffs may, moreover, contain groupingscapable of fixation, such as monoor dihalotriazinylamino, mono-, diortrihalo-pyrimidinyl-amino, 2,3-dihaloquinoxaline-6-carbonylor-6-sulphony1amino, 1,4-dihalophthalazine-6-carbonylor -6-sulphonylamino,Z-halobenzothiazole-S-carbonylor -5-sulphon.ylamino, esterifiedsulphonic acid alkoxyamide and alkoxysulphone groups, sulphofluoride,haloalkylamino, acryloylamino, haloacylamino groups and the like.

The new dyestuffs can be synthesized by various methods. For example,dyestuffs or primary dyestuff products which contain amino or amidegroups and have a reactive hydrogen atom at the amine or amide nitrogen,can be reacted with compounds of the general formula (III) in which Xand Y have the meaning given above and halogen stands for a halogenatom, preferably chlorine, and in the case where primary dyestuffproducts are used, these can be transformed in a suitable manner intothe desired end dyestuffs.

Dependent upon the number of reactive groupings in the dyestuff radicalor in the dyestutf intermediates, which are suitable for the conversion,one or more groupings of the Formula II can be incorporated with thedyestuffs. In most cases, the number in will not exceed 4, but it isalso possible to synthesize dyestuffs, especially those of a highermolecular structure, with more than 4, e.g. up to 8, groupings of theFormula II.

The intermediate products of the Formula III are in part known from theliterature (cf. e.g. J. Org. Chem., 29, 660 [1964]).

Among the great number of dyestuffs obtainable according to the presentprocess those products are especially easily accessible which arederived from amino group-containing azo dyestuffs of thebenzene-azo-ben- Zene, benzene-azo-naphthalene,naphthalene-azo-naphthalene, benzene-azo'aminopyrazole and -pyrazoloneseries and from the hetero-azo-aryl series and the aminoanthraquinoneseries with nuclear-positioned and/or externally linked amino groups, byreaction with compounds of the Formula III.

The new reactive dyestuffs can be produced not only by starting from thefinished dyestuffs; it is also possible to react suitable couplingcomponents which contain amino or amide groups and have at least onereactive hydrogen atom at the amino or amide group, with compounds ofthe Formula III to form preliminary products which are then coupled withsuitable diazonium compounds. Inversely, diazonium compounds whichcontain reactive radicals of the Formula II can be coupled with suitableazo components to produce the azo dyestuffs (I) to be obtained accordingto the present process.

The new dyestuffs are extremely valuable products which are suitable forvarious purposes of application. The water-soluble compounds are ofspecial interest for the dyeing of textile materials containing nitrogenor hydroxyl groups, especially of textile materials of native andregenerated cellulose, further, of wool, silk, synthetic polyamides andpolyurethane fibers. Due to the reactive substituents X or Y in theisothiazole radical, the products are particularly well suited asreactive dyestuffs for dyeing cellulose materials by the methodsrecently disclosed for this purpose. The fastness properties attained,especially the fastness to wet processing, are excellent.

For dyeing cellulose, the dyestuffs are preferably used in an aqueoussolution to which compounds of alkaline reaction, such as alkali metalhydroxide or alkali metal carbonate, or compounds convertible intosubstances of alkaline reaction, such as alkali metal bicarbonate, maybe added. Further adjuvants can be added to the solution, provided theydo not react with the dyestuffs in an undesirable manner. Such additivesare, for example, surfaceactive substances, such as alkylsulphates, orcompounds preventing migration of the dyestuff, or dyeing assistantssuch as urea (for improving the solubility and fixation of thedyestuffs), or inert thickeners such as oil-in-water emulsions,tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to bedyed, for example, by padding on the foulard (short bath) or byprinting, and subsequently heated for some time at an elevatedtemperature, preferably at 40-150 C. Heating can be performed in thehotfiue, in a steaming apparatus, on heated collars or by introducingthe material into heated concentrated salt baths, using these methodssingly or in any sequence.

When a padding liquor or dyebath without alkali is used, the drymaterial is subsequently passed through a solution of alkaline reactionto which sodium chloride or Glaubers salt is added. The addition of saltreduces the migration of the dyestulf from the fiber.

The material to be dyed can also be pretreated with one of the aforesaidacid-binding agents, subsequently treated with the solution or paste ofthe dyestutf, and, finally, fixed at an elevated temperature asdescribed above.

In the so-called cold-batch padding process, the subsequent heating ofthe padded fabric can be saved by storing the fabric for some time atroom temperature. In this process, sodium carbonate is preferably usedas alkali.

For printing materials containing hydroxyl groups, a printing paste isused which consists of the dyestuff solution, a thickening agent such assodium alkinate, and a compound of alkaline reaction or splitting ofialkali when heated, such as sodium carbonate, sodium phosphate,potassium carbonate, potassium acetate or sodium and potassiumbicarbonate, and the printed material is rinsed and finally soaped, ifdesired.

If the dyestuffs contain groupings which form metal complexes, thefastness properties of the dyeings and prints can frequently be improvedby an after-treatment with metal-yielding agents, such as copper salts,e.g. copper sulphate, chromium, cobalt and nickel salts, such aschromium acetate, cobalt sulphate or nickel sulphate.

Textile materials which contain amide groups, such as wool, silk,synthetic polyamide and polyurethane fibers, are generally dyed by themethods customary for this purpose in an acid to neutral medium; a finalraising of the pH value of the dyebath, for example, to a pH of 6.5- 8.5being sometimes of advantage.

The dyestuffs are applied to a synthetic polyamide fabric, for example,as solutions, or, preferably, in the dispersed form and subsequentlyafter-treated, possibly together with preferably small amounts ofacid-binding agents, such as sodium carbonate. Especially advantageousresults are a hieved With those dyestuffs which are insoluble or onlybarely soluble in water. These are worked up by known methods with theaddition of the known assistants into a dyestuif dispersion and appliedas such in the dyebath and/or padding liquor, or in a printing paste.The assistants suitable for this application are, inter alia, compoundswhich prevent the migration of the dyestuff on the fiber, such ascellulose ethers, alkali metal chlorides and sulphates; wetting agents,such as condensation products from ethylene oxide and fatty alcohols orphenols, sulphonated fatty alcohols; solvents, such as thiodiglycol; andthickening agents, such as starch, tragacanth, alginate thickening, gumarabic, etc.

The after-treatment of the dyeings, impregnations and prints obtained onfabrics of polyamide fibers is carried out, preferably, at a temperatureof 501l0 C. for a period of 5-60 minutes. Also in this case the fastnessproperties of the dyeings can sometimes be improved with metal-yieldingagents, such as copper salts, e.g. copper sulphate, or chromium, cobaltand nickel salts, such as chromium acetate, cobalt sulphate or nickelsulphate, provided that the dyestuffs employed contain groupings formingmetal complexes.

The dyeings and prints obtainable with the new dyestuffs are generallydistinguished by good to very good fastness properties, especially byexcellent fastness to wet processing.

The following examples are given for the purpose of illustrating theinvention, and unless otherwise noted, all parts are by weight.

Example 1 To a solution of 34.7 parts of 2-aminonaphthalene-4,8-disulphonic acid sodium salt and 7 parts of sodium nitrite in 300parts of water, are added while cooling with ice, 28 parts by volume ofconcentrated hydrochloric acid, and the mixture is stirred at Ol0 C. for30 minutes. After removing the excess nitrous acid, 10.7 parts of3-aminotoluene dissolved in 10 parts by volurne of concentratedhydrochloric acid and 150 parts of water are added and the coupling iscompleted by neutralizing the mixture to a pH of 3-5. The resultantaminoazo dyestuif is salted out, filtered off with suction, washed andthen dissolved again at a pH of 7 in 700 parts of water with theaddition of a sodium hydroxide solution. The aqueous solution is thenmixed with 21.6 parts of 3,5 dichloro 1,2 isothiazole-4-carboxylic acidchloride (B.P. 102 C./8 mm. Hg) dissolved in 50 parts of acetone andvigorously stirred. By the reaction which sets in, the mixture isspontaneously heated to 35-40" C.; the liberated hydrochloric acid isneutralized With a sodium carbonate solution, until free amino groupscan no longer be detected. The resultant dyestufi of the formula S OaNais salted out with parts of sodium chloride, pressed off, washed, anddried at 40-50 C. in a vacuum. It is a yellow powder which dissolves inwater with a yellow color.

When a cellulose fabric is printed with a printing paste which contains,per kilogram, 15 g. of the dyestuff, g. of urea, 300ml. of water, 500g.of alginate thickening (60 g. of sodium alginate per kg. of thickening),2 g. of sodium hydroxide and 10 g. of sodium carbonate, and which hasbeen made up with water to 1 kilogram, followed by drying, steaming atC. for 8 minutes, rins. ing with hot water and boiling with soap, anintense red-. dish-yellow print of good fastness to washing and light isObtained.

Example 2 rinsed with hot water and treated at the boil for 20 min- 01mol of the copper complex compound of the utes with a solutloncontalning, per liter, g. of M a1'- fonhula sellles soap and 2 g. ofsodium carbonate. After rinsing and drying, an intense reddish-yellowdyeing of good Naoas SOaNa 5 fastness to wet processing, rubbing andlight is obtained. In the following table the diazo components and theNHZ coupling components having linked thereto through the I amino groupthe reactive component 3,5-dichloro-1,2- NZN isothiazole-4-carboxylicacid chloride are listed, from which dyestuffs can be synthesizedfollowing the pro- Naoas 0 Cu 8103M cedure given in Examples 13; theshades obtained by one of the methods of application described above arealso stated in the table.

Example Number Diazo component Coupling component Shade tearnestnesstenant221% teen-sen rr e 61'"I2-aminonaphthalene-5I7-disulphouicacidr """:1j::j d 6 y""'j;:;;1:11jjj: D31 7. Z-aminonaphthalene-G,8-disulphonic acid do Do.8- 4-aminoazobenzeue-l.4-disulphouie acid do Brown-yellow 9.2-(3-sulpho-4-amino-phenyD-G-methylbenzo d mow, 12-aminonaphthalene-4.8-d1sulphomc acid l-amino acetyla nobenzene D0. 11..d0 Aniline Do.

(prepared according to the instructions of German patent Example 12specification No. 1,117,235 by coupling diazotized 1-amino-8-[benzene-sulphonyloxy]-naphthalene-disulphonic Into a solutionof 36.5 parts of the sodium salt of acid-[3,6] in a soda-alkaline mediumwith the equivalent 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in100 amount of 2-acetylamino-5-hydroxynaphthalene-disulparts of water areintroduced with good stirring, 21.6 phonic acid-[4,8], conversion of themonoazo compound parts 0f 3,5 dichloro-1,2-isothiazole-4-carboxylic acid.into the copper complex by oxidative coppering and Chloride, and themixture is stirred at 20-40 C., while hydrolysis f th acetyl d b l h lcontinuously neutralizing the liberated hydrochloric acid is dissolvedin 2500 parts by volume of water at C. to a P of until free amino groupscan no longer p t a H f 6. 6 5 d i d at hi temperature i h a detected.The dyestuff intermediate thus obtained is cousolution of 0.1 mol of3,5-dichloro-l,2-isothiazole-4-car- Pled, after diluting it with 600Parts of Watfil' and boxylic acid chloride in '50 ml. of acetone. Duringcon- 12 P? of S0dh11'h cafhohflte, at With densation a pH of 6-6.5 ismaintained by the addition of 35 Pa f dlaZOtlZed zamlnobehzene'sulphohicacid (118- a sodium carbonate solution. When the reaction'is com- Solved200 Parts of f The dyestufi formed at a pleted, the dyestuff is saltedout and isolated. After dryfinal P of about 7 and havlhg thti formula pHof 7-8, 46 parts of the dyestutf obtained by coupling ing, the dyestutfis a dark powder which dissolves in water with a blue color.

100 parts by weight of a cotton fabric are padded on 40 SOsNa HO NH-OCC-CCl the foulard at room temperature with an aqueous solu- I I I l l,tion containing 2% of the dyestuff, 15 g./liter of sodium -N=N- hydrogencarbonate and 150 g./liter of urea, dried inter- NaO S S mediately,heated at 140 C. for 10 minutes, then rinsed sO Na and boiled with soap.The fabric is dyed in very clear blue shades fast to'wet processing.

Example 3 is salted out with 100 parts of sodium chloride, filtered In300 parts of water at C. are dissolved at a off with suction, washed anddried at 4050 C. in a vacuum. The dyestutf forms small red needles whichdiazotized 2-aminonaphthalene-4,8-disulphonic acid with have a metallicluster and which readily dissolve in water B-methylatnino-toluenefollowing the procedure of Exam- Wit a r d C I r.

ple 1, and mixed in the presence of excess sodium acetate When a fabricof cotton or regellel'atfid 0611111086 is or calcium carbonate at 3540C. portionwise with a dyed or Printed With this dyestuff y e of heethods total of 31 parts of 3,5-dichloro-1,2-isothiazole-4-carbox-'described in Examples 1 clear b1uish-red dyeings and ylic acid chloride,and stirred at the same temperature, P of good fasthess t0 WetProcessing, rubbing, and

until a sample no longer shows a change of color when light areohtaihedacid is added. The resultant dyestuff of the formula Equallygood results are Ohtalhed y the followmg process: SIOBNa 0 b 50 grams ofcotton skein are dyed in 1 liter of a dye- II ath containing 1.5 g. ofthe above dyestuif by raising -fi m the temperature from 20 C. to about40 C. within 30 1 minutes while adding a total of 50 g. of sodiumcarbonate 3 S and treating at the same temperature for 60 minutes. I gAfter rinsing, boiling with soap and drying, a bluish-red S03 a 5 dyeingof good fastness to wet processing, rubbing, and is salted out, filteredoff with suction, washed and dried. light is Obtained Cotton fabric isimpregnated Witha Solution at In the following table the shades offurther dyestuffs 20-25? Which contains, P liter of liquor, 20 of arelisted, which can be synthesized from the likewise The above dyestuffahdJ0-5 g. of a hohdohlc Wetting agent. mentioned diazo components andcoupling components -ga p ly y hleyl alcohol) as Well as 150 havinglinked thereto through the amino group the rev t and 15 gof SodiumbiCaTh0hate- The fabric is active component of the foregoing example, inanalogy subsequently squeezed between two rubber rollers to a with theinstructions of Example 12 or also by reaction of moisture content ofabout After an intermediate the corresponding aminoazo dyestuffs withthe reactive drying at 506(l C., the material is heated at C. component,and which can be dyed or printed on cellulose for 10 minutes, and thedyeing thus obtained'is thoroughly 75 materials by one of the methodsdescribed above.

Example Number Diazo component Coupling component Shade 13l-aminobenzene-Z-sulphonic acidl-(3-aminobenz0ylamino)-8-hydroxynaphthalene-3,6- Red.

disulphonic acid. 14 l-amino:2-carboxybeuzene4-sulphonic acid1-amin0-8-hydroxynaphthalene-li,(idisulphonie acid Red. 15l-amino-4-methylbenzene-2-su1phonic acid do Red. 161-amino-3-(2-[4"-sulphophenylamino]-4-cl1lor0triazinedo Red.

1 ,3,5-yl 6)-aminobenzene-6-sulphonic acid. 17l-aminobenzene-Z-sulphonic acid2-an1ino.5-hydroxynaphthaleue-7-sulphonic acid Orange. 181-amino-3-(2-[4-sulphophenylamino]-4-methylamino- Do.

triazine-1,3,5-yl-6)-aminobenZene-fi-sulphonic acid 19l-aminobenzene-Z-sulphonic acid2-methylamin0-5-hydroxy-uaphthalene-7-sulphonic acid Do. 20l-amino-4-acetylamino-ti-sulphonic acid. d0 Scarlet, 21 do2-an1iuo:5-hydroxynaphthaleuc-7-sulphonic acid Do.

Example 22 Into a solution of 21 parts of the sodium salt of 1,3-diamin0benzene-6-sulph0nic acid in 100 parts of Water, are introducedwith good stirring 21.6 parts of finely powdered3,5-dichloro-1,Z-isothiazole 4 carboxylic acid chloride, and the mixtureis stirred at 20-40 C., while continuously neutralizing the liberatedhydrochloric acid to a pH of 6-7, until a sample, when diazotized andcoupled with 1-hydroxy-naphthalene-4-sulphonic acid, gives a clearyellowish-red coloration. The dyestuff intermediate formed is directlydiazotized, after the addition of ice, with 7 parts of sodium nitriteand 28 parts of concentrated hydrochloric acid and subsequently combinedwith a previously prepared solution of 47 parts of the sodium salt ofl-benzolyamino-8-hydroxy-naphthalene- 3,6-disulphonic acid and 12 partsof sodium carbonate in 200 parts of water, whereupon coupling takesplace and the dyestuif of the formula is formed, which is salted out,filtered out, filtered oif with suction, washed and dried at 4050 C. ina vacuum. The dyestufi? readily dissolves in water with a red color andyields clear bluish-red dyeings and prints on cellulose materials by oneof the methods described above.

In the following table, there are listed the shades and the pH value ofthe coupling medium of dyestuifs which are produced in analogy with theinstructions of Example 22 from the coupling component and a diazocomponent containing a further, preferably acylatable, amino group, andlinked with the reactive component of the foregoing example through anamino group. The methods mentioned above can be used for dyeing andprinting cellulose materials with the dyestuffs of the table.

Example 35 In 1500 parts of water are dissolved at a pH of 7, 51.6 partsof the dyestuif of the formula is salted out, pressed off, washed anddried at 40-50 C. in a vacuum. Fabrics of cellulose materials can bedyed with this dyestufi' by one of the methods mentioned above in rubyshades fast to wet processing, rubbing, and light.

In the following table there are listed the heavy metal complexes offurther aminoazo dyestuifs linked with the reactive component of theforegoing example through the amino group as well as the shades of thesedyestufis on cellulose materials. The production of the aminoazodyestuifs and their metal complexes and the reaction of the latter withthe reactive components can be carried out in analogy with theinstructions of Example 35.

pH of Example coupling Number Diazo component Coupling component mediumShade 23 1,3-diaminobenzene-i-sulphonic acid2-aminonaphthalene-5,7disulphonic acid 4-5 Orange.

do 2-amln0naphthalene-3,G-disulphonic acid.-. 4-5 Do.2-N-methylamino-8-hydroxynaphthalene-fi-sulphonlc aci 4-5 D0.1,(3-5-dichloro-1,2-thiazo1e-4-carbonamido)-8- 7-8 Red.

hydroxy-naphthalene-li,S-dlsulphonic acid.1-(2,4-dihydroxy-triazin-1,3,5-y1-6-amino)-8-hyd.roxy- 7-8 Red.

napthalene-3,6-disu1phonic acid.1-(3-,5-diehloro-l-2-thiazole-4-carbonamido)-8-hydroxynaph- 7-8 Red.

thalene-3,6-disulphonic acid. 2-hydroxy-naphtha1ene-3,6-disu1phonic acid8 Scarlet. 1-(3-sulphophenyl)-3-methylpyrazolene-5 6 Yellow.1-(2,5-dichloro4'-su1phophenyl)-3-methylpyrazolon 6 Do. do1-(5,7-disulpho-naphtyhl-2-)-3-methylpyrazolone-5 6 Do.1,4-dicniiiiobcnzcne-3-sulphonic aci l.2-amino-8-hydroxy-naphthalene-o-sulphonic acid 4-4.5 Rod. 34 doZ-acctalymino-5-hydroxynaphthalene-7-sulphonica 6-7 ScarletComplexlinked Example heavy Number .Aminoazo dyestufl metal Shade 361-hydroxy 2-aminobenzeue4,G-disulphonicacid-*Z-amino-5-hydroxy-naphthalene-7-sulphonic acid. Cu Ruby.

l-hydroxy-2-amin0benzenci-sulphonic acid-2-etl1ylamino-5-hydroxyuaphthalene-7-sulphonic acid. Cu Do.l-arniio-2-hydroxyc-nitro naphthaleneA-sulphouic acid-2-amino-5-hydroxynaphthalene-7-sulphonic Cu Do.

acl ..d Cr Greenish grey. 40 l-amliio-2hydroxy-5methyl-sulphonyl-benzene- 1-amino-8-hydroxy-naphthalene-B,6-dissulphonieCu Violet.

acl 41 do C0 Grey -.d0.. Cr.-- Greenish-black.1-an1ino-2-methylbenzenei-sulphonic acid1-amino-2-hydroxy-5-methylbenzene 1-amino-8- Ct Do.

hydroxy-naphthalenei,6.disulph0nic acid.(l-amino-Z-chlorobenzene-4-sulphonic acid1-hydroxy-2-acetylaminobenzene), saponified,- 1- Cu Navy blue.

amino-8-hydroxy-naphthalene-3,fi-disulphonic acid. .d0 00..........Grey. 46 1-amino-8-hydroxy'naphthalene-i-sulphonic acid1hydr0xy-2,6-diamlnobenzene-isulphonic aeid-+ Co Black.

1,3-dihydroxybenzene. 47 1-amino-8-hydroxy-naphthalene-3,6-disulph0nicaeid+-1-hydroxy-2,G-diarninobenzeneA-sulphonic Co Do.

acid 2-hydroxynaphthalene. 48 1-amino-8-hydroxynaphthalenebsulphonicacid l-hydroxy-2,6-d1aminobenzene4-sulphonic acid Co Do.

3'methyl-pyrazolone (5) Example 49 Thecopper-phthalocyanine-tetrasulphochloride freshly prepared in the usualmanner by the action of chlorosulphonic acid and thionyl chloride oncopper-phthalocyanine, or of the isomericcopper-phthalocyanine-tretrasulphochloride synthesized from1-sulphobenZene-3,4- dicarboxylic acid via the correspondingcopper-phthalocyanine-tetrasulphonic acid, 96 parts (referred to 100%goods), is suspended in the form of the moist, thoroughly washed suctionfilter cake in 500 parts of water and 500 parts of ice, a solution. of50 parts of the sodium salt of 1,3-diaminobenZene-4-sulphonic acid in500 parts of water is added and the pH value is adjusted to 8.5 withsodium carbonate. The suspension is stirred at room temperature for 24hours a pH, value of 8.5 being constantly maintained by the continuousaddition of sodium carbonate. The resultant condensation product isprecipitated at a pH of 1-2 by the addition of sodium chloride, filteredoff with suction, washed and then redissolved neutral in 1000 parts ofwater. A solution of 65 parts of3,5-dichloro-1,2-isoethiazole-4-carboxylic acid chloride in 100 parts ofacetone is added dropwise with intense stirring to the blue solution,and the mixture is stirred at 3040 C., while continuously neutralizingthe liberated hydrochloric acid to a pH of 5-7, until free amino groupscan no longer be detected. The reactive dyestulf of the formula thusobtained is salted out, washed and dried at 30-40" C. in a vacuum. It isa dark blue powder which dissolves in water with a blue color and dyescotton and regenerated cellulose by one of the dyeing or printingmethods mentioned above, in clear blue shades of good fastness to wetprocessing, rubbing, and light.

Instead of 96 parts of copper-phthalocyanine-tetrasulphochloride, therecan also be used 87 parts (referred to 100% goods) of the copperornickel-phthalocyanine trisulphochloride obtainable by the action ofchlorosulphonic acid on copperor nickel-phthalocyanine, in the form ofthe moist suction filter cake thoroughly washed with ice-water theprocedure being otherwise the same ts that of Example 49; reactivedyestuifs yielding clear blue shades are then likewise obtained.

By following the procedure of Example 49, but starting from 87 parts ofcopper-phthalocyanine trisulphochloride and using, instead of 50 partsof the sodium salt of 1,3-

diaminobenzene-4-sulphonic acid, 90 parts of the sodium salt of4,4-diamino-dipheny1-2,2'-disulphonic acid or 90 parts ofthe sodium saltof 4,4-diaminostilbene2,2'-disulphonic acid, reactive dyestuifs areagain obtained which dye cellulose materials by one of the methodsphenylamino) -anthraquinone-2,5-

mentioned above, in clear blue shades fast to wet processing, rubbing,and light.

When starting from 4,4,4" ,4" -tetraphenyl-Cuphthalocyanine, there isobtained after su1phochlorination, reaction with1,3-phenylene-diamine-4-sulphonic acid and acylation with3,S-dichloro-isothiazole-4-carboxylic acid chloride, a reactive dyestulfwhich dyes cellulose materials in the presence of acid-binding agents inclear green shades fast to wet processing and light.

Example 50 In 700 parts of water are dissolved 71 parts of theamino-anthraquinone dyestuff obtained by the recation of1-arnino-4-bromoanthraquinone-2-sulplhonic acid with excess4,4-diamino-diphenyl-2,2'-disulpl1onic acid and 27 parts of3,S-dichloro-isothiazole-4-carbzoxylic acid chloride are added at 2030C. with good stirring, and a pH of 67 is maintained by the continuousaddition ofa sodium carbonate solution. When amino groups can no longerbe detected, the resultant dyestuff of the formula is salted out,filtered off with suction, washed and dried at 40 C. in a vacuum. Itdyes cotton and regenerated cellulose by one of the methods mentionedabove, in blue shades fast to wet processing, rubbing, and light.

By proceeding as described in Example 50, but using, instead of 71 partsof the starting dyestulf there employed, equivalent amounts of one ofthe following derivatives of 1amino-4-(aminoarylamine)-anthraquinone-2-sulphonic acid, similardyestuffs are obtained in the dyeings which are likewise blue and havefastness properties similar to those of the dyestuff obtained above:1-amino-4-(4'- amino 2'-sulphophenylamino)-anthraquinone-Z-sulphonicacid, 1 amino 4-(4'-aminophenylamino)-anthraquinone- 2,6-disulphonicacid, isomeric mixture of l-amino-4-(4- aminophenylamino)anthraquinone-2,S-and -2,8-disulphonic acid, isomeric mixture of1-amino-4-(4-amino-2- sulphophenylamino)-anthraquinone-2,5- and-2,8-disulphonic acid, isomeric mixture of l-amino-4-(3'-aminoand acid,l-amino-4-(3- aminophenylamino) anthraquinone- 2,6-disulphonic acid,1-amin-o-4-(3'-amino-4-sulphophenylamino)-anthraquinone-Z-sulphonicacid. With l-arnino- 4 (4-[4"-amino-2"-sulphophenyl]-aniinophenyl)anthraquinone-2,6-disulphonic acid, reactive. dyestuffs are obtainedwhich dye in bluish-grey shades.

-2,8-disulphonic 1 1 Example 51 By proceeding as described in Example35, but using as starting material, instead of the copper-containingaminomonoazo dyestufi there employed, the equivalent amount of thechrominum complex of the aminoazo dyestuff obtained by couplingdiazotized 1-amino-2-hydroxy- 3-chlorobenzene-5-sulphonic acid with1-[3-(3-amino phenyl)] sulphonylimidosulphonyl-phenyl-3-methylpyrazolone-(S), a reactive dyestuff is obtainedwhich dyes cellulose materials by one of the methods described above, inyellow-brown shades of good fastness to wet processing, rubbing, andlight.

Example 5 2 In 3000 parts by volume of water is dissolved at a pH of 6,0.1 mol of the copper complex compound of the formula SO Na S OgNa 110 s--Cu This solution is combined at a temperature of about 30 C., whilestirring, with a solution of 21.6 parts (0.1 mol) of3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride in acetone. Themixture is stirred until the condensation is completed, the dyestufi? isseparated by the addition of a little sodium chloride and isolated. Theresidue is washed with acetone and dried at room temperature underreduced pressure. A dark powder is obtained which dissolves in waterwith a green color nad dyes cotton by the methods described in Examples1-3, in green shades.

A cotton fabric is impregnated with a solution at 20 25 C., whichcontains, per liter of liquor, 25 g. of the above dyestuff and 0.5 g. ofnon-ionic Wetting agent (e.g. a polyethoxylated oleyl alcohol), 150 g.of urea and 20 g. of sodium carbonate. The fabric is subsequentlysqueezed between two rubber rollers to a moisture content of about 100%.After an intermediate drying at 5060 C., the material is heated at 140C. for 10 minutes and the dyeing thus obtained is thoroughly rinsed withhot water and treated at the boil for 20 minutes with a solutioncontaining, per liter, 5 g. of Marseilles soap and 2 g. of sodiumcarbonate. After rinsing and drying, a green dyeing of good fastness towet processing, rubbing, and light is obtained.

Clear red shades of good fastness properties are also obtained oncellulose materials by one of the other dyeing or printing processesdescribed in Examples 1-3, 12, and 22.

Example 53 In 2000 parts by volume of Water is dissolved at a pH of 6-,0.1 mol of a paste of the aminoazo compound of the formula l HOaS OExample 5 4 An aqueous solution of 0.1 mol of the copper complex of theformula HOaS OCu0 SOaH SOsH prepared according to the instructions ofGerman patent specification No. 1,061,460 or 1,085,988, is combined inthe usual manner with a solution of 21.6 parts of 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride in acetone. A pH of67 is maintained by the addition of Na CO and when the reaction iscompleted, the dyestuff is isolated by salting out. In the dry state, itis a dark powder which dissolves in water with a violet color. Cottonfabrics are dyed in violet shades fast to light and wet processing.

Example 55 In 150 parts of water are dissolved 27.5 parts of 2-methylamino-S-hydroxynaphthalene 7 sulphonic acid sodium salt, mixedwith 21.6 parts of 3,5-dichloro-1,2 isothiazole-4-carboxylic acidchloride and stirred at 35- 40 C. for 30 minutes, while continuouslyneutralizing the resultant hydrochloric acid to a pH of 4-6 with a totalof 34 parts by volume of a 16% sodium carbonate solution. The acylationis completed after about 2 hours, the pH is 6 and changes no more.

30 parts of sodium bicarbonate are then added, and a diazo suspensionfrom 34 parts of the disodium salt of 2-aminonaphthalene-1,7-disulphonicacid in 200 parts of water is added dropwise at 40 C. within 15 minutes.The orange colored reactive dyestulf immediately formed, of the formulais further stirred for one hour, then completely separated by theaddition of parts of sodium chloride, filtered off, washed with a dilutesodium chloride solution and dried at 45 in a vacuum. The dyestuif dyescellulose materials by the methods mentioned above, in reddishorangeshades of very good fastness to Wet processing, and good fastness tochlorine.

By using in this example, instead of 21.6 parts of 3,5-dichloro-1,2-isothiazole 4 carboxylic acid, equivalent amounts of3,5-dibromo-1,Z-isothiazole-4-carboxylic acid bromide, a reactivedyestuff is obtained which dyes in orange shades and the dyeingproperties are similar to those of the corresponding 3,5-dichloroderivative.

Orange to red reactive dyestuffs are obtained in an analogous manner byacylation of the aminonaphtholsulphonic acids listed in column 3 of thefollowing table with 3,5-dichloro-1,2-isothiazole-4-carboxylic acidchloride and coupling the resultant acylaminonaphthol-sulphonic acidswith the diazo components mentioned in column 2.

NaOaS Example Shade on Number Diazo component Aminonaphtholsulphonicacid cotton 56 2-aminonaphthalene-lfl disulphonic acidZ-ethylamino--hydroxynaphthaleno-7-su1phonic acid 4 444 Orange.

57 do Z-(li-laydroxyethylamino)-5-hydroxynaphthalene-7-sul.phonic Do.

-r- Z-amino-5-hydroxynaphthalene-7-sulphonic acid-. Do.2-amino-5-hydroxynaphthalone-1,7-disu1phonic acid. Do.2-arnino-8-hydroxynaphthalene-fi-sulphonic acid. Scarlet.2-amino-8-hydroxynaphthalene-3,6-disulphonic ac Do.Z-methylanuuo-5-hydroxynaphthalene-7-sulphonic a Orange.2-ethylamino-5-hydroxynaphtl1alene-7-sulphonic acid. Do.Z-(fi-hydroxyethylamino)-5-hydroxy-naphthalene-7-sul D0.

phonic acid. 2-amino-5-hy droxynaphthalene-Tsulphonic acid Do. 2-amlno-5hydroxynaphthalene-l,7-disu1phonic acid Do. Z-amino-S-hydroxynaphthalene-Gsulphonic acid. Scarlet.2-amino-8-hydr0xynaphthalene-3,6-disulphonic acid Do.2-amino-5-hydroxynaphthalene-7-sulph0nic acid. Orange.2-metl1y1amino-5-hydroxynaphthalone-7-sulphonic a Do.2-amino8-hydr0xynaphthalenafi-sulphonic acid. Scarlet.2methylamino-hydroxynaphthalene-7-sulphonic a Orange2-(B-hydroxyethy1amino)-5-hydroxynaphthalene-7-su1- Do.

phonic acid. 74 do 2amino-8-hydroxynaphthalene'fi-sulphonic acid e.Scarlet. Z-amino-B-hydroxynaphthalene-S,G-disulphonic acid Do. do2-an1ino-5-hydroxynaphthalene-l,7-disulphonic acid- Orange. 772arninonaphtha l-amino-S-hydroxynaphthalene-Ii,6-disulpho11ic acid-Bluish-red. 78 do l-amrno-S-hydroxynaphthaleno' i,fi-disulphonic acidDo. 79 Z-aminonaphthalene-l,5disulphonic acl1ammo-Shydroxynaphthalene-ii,fi disulphonic acid Do. 80 ol-amino8-hydr0xynaphthalene-4,6-d1sulphon1c acid Do. 811-amrno-8-hydroxynaphthalene-6-sulphonic acid Do. 821-am1no-8-hydroxynaphthalenc-B,G-disulphouic acid Do. 83 .dol-amino-8-hydroxynaphthalene-4,6-disulphonic acid Do. 84.-. dol-amino-8:hydroxynaphthaleno-G-sulphonic acid. Do. 85 -aminonaphtha1ene-.-...d 0 Do. 86.. l-arnino-4-chlorobenzenesulphonic acid1-arn1no-8-hydroxynaphthalene-3,6-d1sulphon1c ac1 Do. 87..l-amino-2-methoxybcnzeue-S-sulphonic acid. 881-aminobenzene-Z-carboxylic acid-4'sulphpn1c acid 89.-l-amino-4-acetylaminobenzene-Z-sulphomc acid 90 i .do

Example 91 dyestufif obtained by coupling diazotizedZ-amino-naphthalene-2,6,8-trisulphonic acid with 3-acetylamino-anilinein an acetic acid medium, and the mixture is stirred at 45 C. for 6hours, a pH of about 6 being maintained by the continuous addition of asodium hydroxide solution. The partially precipitated acylation productis completely separated at a pH of 6.5 by the addition of 100 parts ofsodium chloride, and filtered off. For purification, the dyestutf thusobtained can be redissolved in 2500 parts of water at 60 C., clarifiedand separated again by salting out the warm filtrate with 350 parts ofsodium chloride. The dyestuff has the formula In 450 parts of water aredissolved at a pH of 7, 56.8 parts of the diaminoazo dyestufi obtainedby coupling diazotized l-amino 3 acetylaminobenzene-6-sulphonic acidwith 2-aminonaphthalene-5,7-disulphonic acid in an acetic acid mediumand subsequent alkaline or acidic 35 hydrolysis of the acetylaminogroup. -After the addition of 21.6 parts of3,5-dichloro-1,2-isothiaZole-4-carboxylic acid chloride, the mixture isstirred at C. for about 3 hours, while continuously neutralizing theliberated hydrochloric acid with a sodium carbonate solution. When theacylation is completed, the resultant dyestutf of the formula SIOaNa SONa NH:

l N=N- NHC O-C--OCl 45 1% N=N ol-c NaOsS S0 Na NHO0CH, C1-C-CCOHN -SOaNal 1431 and after filtering 01f, drying at 45 C. and grinding, it isNaoss a yellow powder which readily dissolves: in water, with a S yellowcolor and dyes cellulose fibers by one of the dyeing methods mentionedabove, in the presence of acidis salted out, filtered 0E, againdissolved in 4000 parts of b n ng agents, in very fast reddish-yel1owshades. Fast Water at 60 C., filtered and separated from the filtrate inyellow Shades are o Obt ned On W001 and polyamide a completely purestate by the addition of 400 parts of fi sodium chloride. The dyestutfis dried in the usual man- S m a dyestufi's are obtained by proceedingas dener at 45 C. in a vacuum. It dyes cellulose materials by scribedabove, but using, instead of Parts of one of the methods mentionedabove, in fast yellowish- 2-acety1amin P Y P 3, orange shades.trisulphonic acid sodium salt, corresponding quantities E l 92 60 of theaminoazo dyestulf obtained from the amino compounds given in column 2and the coupling components 3,S-dichloro-1,2-isothiazole-4-carboxylicacid chloride, given in column 3 in the usual manner by diazotizing and21.6 parts, is added to a neutral solution in 500 parts of coupling inan acetic acid medium, and acylating with water of 60 parts of thetrisodium salt of the aminoazo 3,5-dichloro-1,2-isothiazole-4-carboxylicacid chloride.

Example Number Diazo component Coupling component Shade on cotton 932-aminonaphthalene-1,fi-disulphonic acid1-amino-3-methyl-o-methoxybenzene Strongly reddishyellow.

94 ..do 1-amino-3-methylbenzene Yellow.

l-aminonaphthalene-fi-sulphonic acid Reddish-yellow. Y

. 1-arnino-3-acetylaminobenzene ellow 3-aminophenyl urea Do. (1l-amino-3-hydroxyacetylaminobenzene Do. 99Z-aminonaphthalene-5,7-d1su1ph0nic acid1-amino-3-methyl-fi-methoxybenzene strolriglyreddishye ow. 100 do1-aminonaphthalene-7-su1phonic acid Reddish-yellow. 101.dol-arnino-3-acetylaminobenzene Do. 102. do- E-aminophenyl urea Do. 1 3o l-amino-3-hydroxyacety1aminobenzene Do.

Example Number Diazo component Coupling component Shade on cotton 1041-aminonaphthalene-3,7-disulphonic acidl-amino-3-methyl-fi-methoxybenzene strorlllglyreddishye 0w. 105 dol-amino-3-methylbenzenc Reddish-yellow. 106 .dol-aminonaphthalene-fl-snlphonic acid Do. 107 Z-aniinonaphthalene-3,oclisulphonic acid 1-amino-3-methylbenzene D0. 108 lol-amino-3-methyl-G-methoxybcnzenc Strongly reddishy w. 100 do1-amino-3-acetylaminobenzene Reddish-yellow.

.do... B'aminQphenylurca Do. .do. l-a1nino-3-hydroxy-acetylaminobenzone.Do. ,do l-aini1i0naphthalene-firsulplionic acid Do...-aininonap11tl1alone-6,S-drsulphonicacid.l-ami1'1o-3-acetylan1in0benzene Do. 114 dol-znnii1o-2-metl1oxy-naphthalcne-6-sulph0nic acid Strongly reddishy ow.115 do 1-aminonaphthalene-fi-sulphonic acid Reddish-yellow.

2-ami11onaphthalene-4,s-disulphonic acid 1-aminonaphthalene-6-sulplionicacid Yellow. d 1-aminonaphthalene-7-sulpl1onie acid Do. 113 do 1-arnino-2-methoxy-naphthalene-G-sulphonic acid Strofigly reddishye 0w. 119do l-methylamino-B-methylbenzene Yellow. l-ethylamino3-methylbenzene Do,N-mcthylaniline Do, N-ethylaniline Do. N-(fi-liydroxyetliyl)-aniline Do.

N-butylaniline. Do.

Anine Redgish-yellow.

1-amin0-3-methyl 3-aminophenyl urea Do.1-amino-3-hydroxyacetylainmobenzene Do.l-amino3-acetylamino-6-methoxybenzene Yellowish-orange.

Reddish-yellow.

1-amino-3-acetylamino-64nethylbenzenel-an1ino-3-methanesulphonyl-aminobenzene. o.

2,5-dimethoxyaniline YelloWiSh-orange.

. 3-11iethyl-fi-methoxyaniline Do.

N-methylaniline Reddish-yellow.

. N-ethylaniline..- D

N-butylaniline Do. N-(B-hydi'oxyethyl)-aniline Do.3-(N-etl1ylaniino)-tolncne-o Do, B-aminotoluene Do.

banii11o-2,5-din1ethylbenzune. Strong reddishyellow.

l-aniiiio-2-metl1oxybenzene l-amino-3-methoxybenzeue.

1-etl1ylamino-3-meth0xybcnze 1-aminonaphtl1alene-6-sulphonica l) oReddish-yellow.

do 1-aminonapththalene-7-sulphonic acid Do.-aminonaphthalene-4,6,8-trisulphonic aci Lamino-3-methylbenzene D0. 0l-amino-3-acetylaminobenzcne. Do. 1-aminonaphthalene-2,4,7-trisulphonicacid 1-amino-3-methylbenzeue V Yellow. (1 1-aminonaphthalene-6-sulphonicacid Do.

1-amino-3acetylaminobenzene Reddish-yellow, 3-aminophenyl urea Do.1-amino-3-hydroxyacetylaminobcnzene Do. Nmothylaniline Do.N-ethylaniline Do. N -butylaniline Do. N-(B-hydroxyethyl)-anil1ne Do.1-(N-othylainino)-3-methylbcnzcne Do. l-aminonaphtlialenc-6-sulphonic acDo. l-aminonaphthalene-7-sulphonic acid Do. l-amino-S-methylbenzeneYellow l-amino-3-acetylaminobenzene l-amino-Z-methoxy-S-methylbenzene.1-amino-2,5-dimethoxy benzene disulphonic acid1-amin0-2-methoxy-5-methylbenzene D Do. Reddish-yellow.

Example 165 hydrochloric acid to a pH of 5-6 with a sodium carbonatesolution, until free amino groups can no longer be deg z ggz f gi 33: 1adlssolved neutral 65 pans of tected. The resultant reactive dyestuff ofthe formula 00u-0 O( 3uO l I E!) I E 55 NaOaS- N=1 I-3NHo-o-co1 Na0 sN=N N112 II II ClC N NaOaS N&O3S I S some soaNa 60 is salted out,filtered off, washed and dried at 4050 C. prepared by couplingdiazotized l-hydroxy-Z-aminoben- The dyestufl dyes cellulose materialsin very fast ruby zene-4,6-disulphonic acid with 2-arnino-8-hydroxynaphshades by one of the methods described above. thalene-6-sulphonic acidand coppering the resultant azo Dyestufis of similar properties areobtained in a mandyestufr". 21.6 parts of3,S-dichloro-1,2-isothiazole-4-carner analogous to the method describedabove from the boxylic acid chloride are added and the mixture isstirred 5 copper complexes of the azo dyestuffs prepared from the at40-45 C., while continuously neutralizing the liberated diazo and azocomponents listed in the following table.

Example Shade 011 Number Diazo component Coupling component cotton2-methylamino-5-hydroxy-naphthalene-7-sulpl1onic acid Ruby.2-ethylamino-5-hydroxynaphthalene-7-sulphonic acid 0. 2(3-hydroxyethylamino)5-hydroxynaphthalcne-7- Do.

sulphonic acid.

2-amino-8-hydroxynaphthalene-3,6-disulphonic acid Do.2amino-5-hydroxynaplithalene-l,7-disulphonic acid. D0.2-amino-8-hydroxynap hthalene-3,6-disulphonic acid. Do.2-methylamino-5-hydroxynaphthalene-7-sulphonie acid D o.Zethylamino-S-hydroxynaphthalenc-7-sulphonic acid Do.

174 .do h Q-(B-hydroxyethylamino)-5-hydroxynapl1thalene-7- Do.

Example Shade on Number Diazo component Coupling component cottonl-amino-8-hydr0xynaphtha1ene-3,6-disulphonic acid Violet.l-amino-8hydroxynaphthalene4,G-disulphonic acid Do. larnin-8-hydroxynaphthalene3,G-disulphonic acid Do.l-amin0-8-hydroxynapthalene-4,fi-disulphonic acid D0l-arnino-8-hydroxynaphthalene-3,G-disulphonic acid1-ethoxy-8-hydr0xynaphthalene3,6-disulphonic acid (i-positionedacctylamino group subsequently saponified)1-hydroxy-2-amino-4-acetylaminobenzene-fi-sulphonic acid...l-amino-S-hydroxynaphthalene-2A-disulphonic acid Blue.

do 1-amino-s-hydroxynaphthalene-2,4,G-trisulphonic acid Do.l-hydroxy-2-amino-6-acetylaminobenzene--sulphonic acid.1-arnino-8-hydroxynaphthalene2,4-disulphonic acid Do.

(ti-positioned acetylamino group saponified) 184;l-amino-2-hydroxy-fi-nitronaphthalenei-sulphonic acidl-amino-s-hydroxynaphthalene-2,4-disulphonic acid D o.

(6-positioned nitro group subsequently reduced to -NH2) 1 85.Laminc-2-hydroxy-6-nitronaphthaleneA-sulphonic acidl-aminc-8-hydroxynaphthalene-2,4,6-trisulphonic acid D0.

(6positi0ned nitro group subsequently reduced to NH2) 1861-hydroxy-2-amino-6-acetylaminobenienei-sulphonic acid-..1-amino-8-hydroxynaphthalene-2,4,6-trisulphonic acid ((S-pcsitionedacetylamino group saponified) Example 187 is isolated in the mannerdescribed in Example 22. The water-soluble dyestuif dyes cellulosematerials by the padsteaming or pad-thermofixing method (at 140 C.) inwhite-dischargeable bluish-red shades which are fast to wet processing,rubbing, and light.

Example 1 8 8 A solution of 19.5 parts of the sodium salt of1-aminobenzene-4-sulphonic acid and 6.9 parts of sodium nitrite in 200parts of water is allowed to run into a mixture of 100 parts of iceand-28 parts by volume of concentrated hydrochloric acid; the mixture isthen stirred at 0-10 C. for 30-minutes and'the excess nitrous acid issubsequently removed. To the diazo suspension thus obtained there isadded at 0-10" C. the cooled and thus partially recrystallized solutionof 26.2 parts of the potassium salt of 1- aminonaphthalene-8-sulphonicacid in 250 parts of hot water and the strongly acidic coupling mixtureis neutralized at -20" C. to a pH of 4 by carefully adding asodiumhydroxide solution. The coupling is rapidly completed; the aminoazodyestulf formed is completely salted out with 100 parts of sodiumchloride, filtered off with suction, washed and redissolved in 400 partsof water at 50 C. at a pH of 6-7. The aqueous solution is mixed with21.6 parts of finely powdered 3,5-dichloro-1,2-isothiazole- 4-carboxylic acid chloride and stirred at 45-50 C. for one hour, whilecontinuously neutralizing the liberated hydrochloric acid to a pH of 5with a sodium carbonate solua so N 111 is salted out with 40 parts ofsodium chloride, filtered off and redissolved in 800 parts of warm waterfor purification. After clarifying the solution, the pure dyestuff isseparated from the filtrate by the addition of -100 parts of sodiumchloride. After filtering off, drying at 45 C. and grinding, a yellowpowder is obtained which readily dissolves in water, with a yellowcolor, and dyes cellulose fibers by one of the dyeing methods mentionedabove in the presence of acid-binding agents in yellow shades of verygood fastness to wet processing, light and chlorine. Fast yellow shadesare also obtained on wool and polyamide fibers.

By proceeding as described above, but coupling, instead of 19.5 parts ofthe sodium salt of 1-aminobenzene-4 sulphonic acid, equivalentamounts'of the d iazo components listed in the following table with1-aminona'plithalene 8- sulphonic acid, followed by acylation with3,5-dichloro- 1,2-isothiazole-4-carboxylic acid chloride, valuableyellow to brown reactive dyestuffs are also obtained.

4-amino-2-acetylamino-azobenzeue-2,5-disulphonic acid Orange- SOsNa gSOsNa (l-aminobenzene-2.5-disulphonic acid coupled with 1-amino-naphthalene-fi-sulphonic acid in an. acidic medium) Shade oncellulose Diazo component fibers S (])aNa S OaNa S OaNa (6,7)

(1-arninobenzene-2,5-disulphonic acid coupled with a technical mixtureof l-aminonaphthalene-G- and -7- sulphonic acid in an acidic medium) S(]);;N a

N=N -NH lolettishbrown. NaaS- S 03N2. s O3N3(l-amino-naphthalene-2,5,7-trisulphonic acid coupled withl-amino-naphthalene-Gsulphonic acid in an acidic medium) S (lhNa ()CHaN=N -NH Reddishbrown. NaOaS- Ha SOaNa(l-amino-naphthalene-2,5,7-trisulphonic acid coupled with1-amino-2-methoxy-fi-mcthylbcnzene in an acidic medium) Example 189 Whena cellulose fabric is printed with a printing paste which contains, perkilogram, 30 g. of the dyestuff described in Example 12, 100 g. of urea,300 g. of water, 500 g. of alginate thickening (60 g. of sodium alginateper kilogram of thickening), g. of sodium carbonate and 10 g. of thesodium salt of 3-nitrobenzene-sulphonic acid and which was made up withwater to 1 kg., subsequently subjected to intermediate drying and thensteamed in a suitable steaming apparatus at 103-115 C. for sec onds,rinsed and boiled with soap, an intense bluish-red print of goodfastness to wet processing, rubbing, and light is obtained.

Example 190 A mixture of the solutions of 65.5 parts each of the 2:1chromium complex and the 2:1 cobalt complex of the dyestuif of theformula NaOaS SOQNa each time, in 400 parts of water, is stirred with 45parts of finely powdered 3,5 dichloro 1,2 isothiazole-4-car- 20 boxylicacid chloride at 45 C. for about 10 hours, whi e maintaining a pH of4.5-5.5. When no more aminoazo dyestuif can be detected bychromatography (Co-complex: blue; Cr-complex: blue-green), the resultantmixture of the two reactive dyestuffs is salted out with potassiumchloride, filtered oil? and dried.

The dyestufi yields on cellulose materials by the padding processes orby printing in the presence of acidbinding agents intense black shadesof very good fastness to wet processing and light.

By proceeding in an analogous manner, but using a mixture of the 2:1chromium-complex and the 2:1 cobalt-complex of the following aminoazodyestuifs, valuable black dyestuffs are likewise obtained.

Coupling Diazo component Coupling component pHl-hydroxy-2-amino-4-nitrobenzene.

1-hydroxy-2-amino-4-nitronapihthalenefl-sulphouic acl l-hydroxy-Si-amlnonaphtha- 9 leI(11e-3,6disulphonic acid. o 9

Example 191 is filtered oil, dissolved warm at a pH of 6-7 in 3000 partsof water and reprecipitated from the filtered solution by the additionof sodium chloride. After filtering oil, drying and powdering, a yellowpowder is obtained, which is readily soluble in water and dyes cellulosematerials from a long bath at 40 C. or by the cold-padbatch process withthe use of sodium carbonate as acidbinding agent, in clear yellow shadesfast to washing, rubbing, and light.

By proceeding as described above, but using, instead of the aminoazodyestuif there employed, equivalent amounts of the aminoazo dyestuifssynthesized from the components listed in the following table, valuablenew reactive dyestulfs are likewise obtained.

In the table, the term saponified means that an acylamino groupcontained in the aminoazo dyestufi was subsequently saponified, whilethe term reduced means that a nitro group contained in the diazocomponent is reduced, after coupling, to the amino group, whereby thedesired aminoazo dyestulf is formed.

pH of EX. Diazo Azo coupling Shade on No. component component mediumcellulose 192.-.. 1-amino-4-nitrobenzene-2sulphonic acid1-(4-sulphopl1enyl)-3-metl1yl-pyrazolone-(5) -6 Yellow.

(i-positioned nitro group subsequently reduced) 193--..l-amino-4-nitrobenzene-i fsulphonic acidl-(4-sulphophenyl)-3-carboXy-pyrazolone-(5) 5-6 Reddish-yellow. 1 o1-(3-sulphophenyl)-3-methyl-5-an1ino-pyrazole.. 6-7 Do. 195.-..l-amino-B-acetyIamino-beuzene-fi-sulphonic acid ..do 6-7 Do.

(3-positioned acetylamino group subsequently saponified) 196-...1-amino-3-acetylamino-benzene-G-sulphonic acidl-(fi-hydroxyethyl)-3-methyl-pyrazolone-(5) 5-6 Do. 197-... 2 moll-amino-3-acetylamino-benzene-tysulphonic acid 1 mol bis-pyrazolone from4,4-bis-hydrazino-dibenzyl- 5-6 Do.

(saponified). 2.2-bisu1phonic acid and aeetoacetic ethyl ester. 198....1 IZIOI Lair?iig-3-acetylamino-benzene-fi-sulphonic acid1-(4-sulphophenyl)-3-carboxy-pyrazolone-(5) 5-6 Do.

sapon 1e 199.... 1-amino-5-acetylamino-naphthalene-3,7-disu1phonic.-...do 5-6 Do.

acid (saponified). l-amino-2-methyl-benzene-4,6-disulphonic acid2-acetylamino-5-naphthol-7-sulphomc acid (saponified). 7-8 Orange.

...do.- 2-acetylamino-8-naphthol-fi-sulphonic acid (saponified) 7-8 Red.

do l-chloig-gpcetylamino-fi-naphthol-7-sulphonic acid (sa- 7-8 Orange.

pon e 203...- 1 aminobenzene-2-sulphonic acidl-acetylaminoig-hiydroxy-naphtha1ene-4,6-disu1phonic 7-8 Red.

ac sapon e 204.--. 2-aminonaphthaleue-3,G-disulphonic acid ..do 7-8Bluish-red. Z-aminonaphtha1ene3,7-disulphonic acid. do. 7-8 Do.2-aminonaphthalene-4,8-disulphonic acid ...do 7-8 D0.Zaminonaphthalene-3,6-disulphonie acidl-acetylamiuo-8-hydroxy-naphthalene-3,6-disulphonic 7-8 Do.

. acid (saponified). Z-aminonaphthalene-4,8-disulphonic acid ..do 7-8Do. 1-amino-4-methoxybenzene-2-sulphonic acid2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7- 7-8 Yellowish-red.

. sulphonic acid (saponified). .do2-(N-acetyl-N-methylamin0)-8-hydroxynaphthalene-(i- 7-8 Red. sulphonicacid (saponified). 211--.- l-aminobenzene-Q-sulphonic acid2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene6- 7-8 Red.

sulphonic acid (saponified). 212.-.. l-aminobenzene-3-sulphonic acid..do 7-8 Red. 213.-.. l-aminobenzenc-i-sulphonic acid.- .do. 7-8 Red.214--.. 1-amino-4-methylbenzene-Z-sulphon a .d 7-8 Red.1-amino-2,4-dimethylbenzene-G-sulphonic a ...do.... 7-8 Red. 216 ..do2-agei1yl-8-hydroxy-naphthalene-fi-sulphonic acid (sapon- 7-8 Red.

1 e 217 ..do Z-acetylamino-S-hydroxyuaphthalene-3,6-disulphonic 7-8 Red.

acid (saponified). 218.-.. 4-aminoazobenzene-3,4-disulphouic acid1-amino-3-acetylaminobenzene 5-6 Yellow-brown. 219 ..do1-amino-3-hybroxyacetylamino-benzene 5-6 Do. 220 .dol-amino-naphthalene-G-sulphonic acid 5-6 Do. 221... .do..1-amino-naphthalene-7-sulpl1onic acid 5-6 Do. 222 .dol-amino-2-(4-amino-2-sulphophenyl-(l 8 Black.

ynaphthalene-B,(i-disulphonic acid.

Example 223 In 1000 parts of water are dissolved 52.4 parts of thedisodium salt of 4-([4"-aminophenyl]-amino)-2'-nitro-diphenyl-amino-3,4'-disulphonic acid and stirred with 21.6 parts 0f 3,S-dichloro-1,2-isothiazole-4-carboxylic acid chloride at 50 C. for 5hours. The liberated hydrochloric acid is continuously neutralized withsodium carbonate to a pH of 4-6. The resultant reactive nitro dyestufiof the formula H l l N02 S OsNa.

is salted out, filtered oil, washed and dried. The dyestuff dyescellulose fibers from a long bath or by one of the customary paddingprocesses in the presence of sodium carbonate as acid-binding agent indeep violet-brown shades fast to wet processing and rubbing.

Example 224 A neutral solution of 54.7 parts of the disodium salt of lamino-4-(2,'-methyl-3'-arninophenyl)-amino-anthraquinone 2,5-disulphonicacid in 1000 parts of water is stirred with 21.6 parts of3,5-dichloro-1,2-isothiazole-4- carboxylic acid chloride at 30 C. for 4hours. The liberated hydrochloric acid is continuously neutralized to apH value of 65-7 with a sodium carbonate solution. When the reaction iscompleted, the resultant reactive dyestuff of the formula (H) NH2 23with 3,5-dichloro-1,Z-isothiazole-4-carboxylic acid chlo ride:

Example Number Water-soluble amino-anthraquinone derivative 225l-aminoA-(3-aminophenyl)-amino-anthraquinone-2,5-

disulphonic acid.

226 1-amino-4-(2-chloro-3-minopheny1)-amino-anthraquinone- 2,5-disulhonic acid.

227 1-amino-4-2-methyl-3-methylaminophenyl)aminoanthraquinone-2,5-disulphonic acid.

228 1-amino-4-(4-aminophenyl)-amino anthraquinone-2,6,3-

trisulphonic acid.

229 1-amino-4-(3-aminophenyl)-amino-anthraquinone-2,6,4-

trisulphonic acid.

230 1-amino-4-(4-aminophenyl)-amino-anthraquinone-2,5,3-

trisulphonic aci 231l-amino-4-(3-aminophenyl)-amino-anthraquinone-2,5,4-

trisulphonic acid.

232 Mixture of 1-amino-4-(3-aminophenyl)aminoanthraquinone-2,45 and-2,4-8-trisulphonic acid furthermore, the derivatives subsequentlysulphonated with 5% oleum at 30 C.

233 1-amino-4-[4-(4-aminobenzyl)-phenyl]-aminoanthraquinone-2-sulphonicacid.

234 1-amino-4-(4-methylaminophenyl)amino-anthraqu'mone-2-sulphonic acid.

235 l-amino-4-(3'-methylamin0phenyl)-amino-anthraquin0ne- 2-sulphonicacid.

236 l-amino i-(2-methylaminophenyl)amino-anthraqumone- 2-su1phonic acid.v

237 1-amino-4-(7-amino-naphthyl-[2])-an1ino-anthraqu1none- 2-sulphonicacid.

238 The condensation product of 1 mol of cyanuric chloride with 1 mol of1,4-diamino-anthrar uinone-2-sulphonic acid, 1 mol ofaniline-2,5-disulphonic acid, and 1 mol of ethylene diamine (one-sided)yields, alter acylation with 3,5-dichloro-1,2-isothiazole-4-carboxylicacid chloride, a violet reactive dyestuff.

Example 239 A solution of 107 g. of a mixture of equal molar portions ofcopper-phthalocyanine-trisulphonic acid-(3,3',3")-mono-(m-amino-p-sulphophenyl)-amide andcopperphthalocyanine-trisulphonicacid-3,3',3)-di-(m-amino-psulphophenyl)-amide is adjusted to 1.3 litersand a pH of 6; 32.5 g. of 3,5-dichloro-1,2-isothiazole-4-carboxylic acidchloride are introduced at 2025 C. While stirring, the temperature israised by 510 C. per hour and finally kept at 4550 C. for several hours.At the same time, a pH of about 6.1-6.9 is maintained by the dropwiseaddition of 3 N NaOH, until on average each dyestuff molecule isprovided with at least one dichloro-isothiazolecarboxylic acid amideradical; this can easily be ascertained by the consumption of sodiumhydroxide solution, on the one hand, and by a determination of aminogroups, on the other hand. The 3,5-dichloro-1,2-isothiazole-4-carboxylicacid chloride can also be introduced in the form of a solution inacetone. For working up, the dyestufr' solution may also be heated atthe stated pH to 80 C. or more, without reducing the capability of thedyestuif to react with cellulose. Separation of unreacted 3,5-dichloro-l,2-isothiazole-4-carboxylic acid and of the saponificationproduct formed therefrom is carried out by filtration or in a separator.The reaction product is precipitated by introducing 150 g. of sodiumchloride per liter of dyestuif solution. The product is filtered offwith suction and dried at about 50 C. in a vacuum or at normal pressure.195200 grams of crude dyestuff are obtained, which still contains about30% of sodium chloride. The common salt can be removed to a great extentby stirring the crude dyestuif with 250 ml. of water and again filteringofi with suction.

The dyestuif dyes cellulose materials by the pad-thermofixing process at140 C. and the pad-steaming process in turquoise shades fast to wetprocessing, rubbing, and light.

The dyestuff mixture used as starting material can be obtained by amethod known as such, for example, by adding 3 mol of2,4-diaminobenZene-sulphonic acid at 0-20" C. and at a pH of about 6.5to an aqueous suspension of a copper-phthalocyanine-trisulphonic acidchloride which is free of sulphonic acid groups, and simultaneouslycatalyzing the saponification with 3 mol of pyridine, whereby theabove-mentioned mixture of Pcsulphonamides is formed.

A similar product is obtained by using as starting material a mixturewhich contains the stated components in a molar ratio of 4:1. Thismixture is obtained from the same copper-phthalocyanine-trisulphonicacid chloride and 2 mol of 2,4-diaminobenzene-sulphonic acid by the sameprocess.

Instead of the stated starting materials there may also be used thosewhich in place of copper contain nickel as the central atom or whichwere prepared from copperphthalocyanine-trisulphonic acidchloride-(4,4',4") or from phthalocyanine-tetrasulphonic acidchlorides-(3,4, 4",4) or -(4,4',4,4") or with the use of otherarylenediamine-sulphonic acids, such as toluylene-diamine-(2,4)sulphonic acid (5), 4,4 diamino dibenzyl-disulphonic acid-(2,2),naphthylene-diamine-(1,5)-disulphonic acid- (3,7). Products of this typeand their production have frequently been described in the patentliterature. Their reaction with 3,5 dichloro 1,2isothiazole-4-carboxylic acid chloride can always be carried out in thesame way.

This applies also to the reaction of 3,5-dichloro-1,2-isothiazole-4-carboxylic acid chloride with the copperandnickel-phthalocyanine intermediates which lead to green reactivedyestuffs and are obtainable, for example, by polysulphochlorination oftetra (3,3',3,3"') (p -toly1- rnercapto)-copper-phthalocyanine withchlorosulphonic acid, condensation of 1 to 2 sulphochloride groups permolecule with 1,3-phenylene-diamine-4-sulphonic acid or1,4-phenylene-diamine-3-sulphonic acid, and saponification of theremaining sulpho-chloride groups; also the homogeneous or mixed aminogroupand sulpho groupcontaining arylation and alkylation products oftriand tetramercapto-copper- (-nickel)-phthalocyanine can be convertedinto valuable green reactive dyestuffs in an analogous manner byacylation of their amino group with3,5-dichloro-1,2-isothiazole-4-carboxylic acid.

Example 240 By proceeding according to the instructions of Example 12,but coupling the dyestutf intermediate obtained in the presence of 12parts of sodium carbonate at a final pH of 7, with the diazo compoundfrom 20.8 parts of 3-chloro-aniline-6-sulphonic acid, in place of thediazo compound from 17.5 parts of Z-aminobenzene-sulphonic acid, areactive dyestuff of the formula I P 0 s 01 NaO S some is obtained, withwhich cellulose materials can be dyed or printed by one of the paddingor printing processes customary for reactive dyestuffs with the use ofsodium carbonate as acid-binding agent, in brilliant red shades fast towet processing.

In an analogous manner there are obtained from the coupling componentslisted in the following table by acylation of their amino group with3,5-dichloro-1,2-isothiazole-4-carboxylic acid'chloride and coupling ofthe resultant dyestuff intermediates with the stated diazo components,valuable reactive dyestuffs with which cellulose materials can be dyedor printed, preferably in the presence of sodium carbonate, in theshades as indicated.

Ex. Coupling No. Diazo component Coupling component pH Shadel-amino-B-hydroxynaphthaleue-B,fi-disulphonie acid '7-8 Violet.

241.-. 1-amino-4-rnethoxybenzene-G-sulphonic acid 242 .do

'7-8 Reddish-Violet.

l-amino-S-hydroxynapl1thalene-4,G-disulplionic acid 243 do2-amin0-frhydroxynaphthalene-l,7-disulphonic acid 7 Scarlet. 244.-..1-amino-schlorobenzene-Z-sulphonic a d 7 Orange. 245-...l-aminobenzeue-3sulphonic acid. 7 Do. 246--.. 1-aminobenzene i-sulphonicacid 7 Do. 247. ..do ydroxy sulphonic acid 7-8 Scarlet. 2484-aminobenzoic acid-(B-sulpho-ethyl l-aminos-hydroxynaphthaleneafi-disulphonic acid 7-8 Red. 249.1-amino-4-sulphoacetylamino-benzene-o-sulp ca d A. 7-8 Violet. 250. 1amino-3-sulphoacetylamino-benzene-tS-sulphonic acid-2-amino-5-hydroxynapththalene-l,7-disulphonic acid 7 Orange 251.1-amino-4-sulphoacetylamino-benzene do 7 Scarlet. 252-.1-aminobenzene-2,4-disulphonic acid1(2-methyl-3-amino-5-sulphophenyl)-3-methy1- 6 Yellow pyrazolone-(5)253--.. 2-aminonaphthalone-4,8-disulphonic acid do 6 D0.

Example 254 aminoazo dyestutf synthesized from the components listed Byproceeding according to theinstructions f Examin the following tablewith 3,S-dichloro-l,2-isothiazoleple 22, but coupling the dyestuffintermediate obtained carboxylic acid chloride:

Ex. No. Diazo component Azo component Shade 256--.. l-amino4-nitrobenzene-2rsulphonic acid (reduced)l-(2-methyl-4-sulphophenyl)-3-methyl-pyrazolone-(5) Yellow. 257... d1-(2,5-disulphophenyl)-3-methylpyrazolone(5) Do. 258 d1-(2-methyl-4-sulpho-6-chlorophenyl)-3-methylpyrazolone (5)- Do. 259...1-(2,5-dichloro-4-sulph0phenyl)-3-methylpyrazolone(5) Do. 260. I-amino--acetylaminobenzene-ti-sulphonie acid (saponified).l-(2-metl1yl-4l-sulpl1ophenyl)-3-methylpyrazolone-(5) Greifilishye 0w.1-(4'-sulphophenyl)-3-methyl-pyrazoloue-(5) Do.1-(2-methyl-4-sulphophenyl)-3-carboxy-pyrazolone-(5 Do,1-(2-chl0ro-4-sulphophenyl)-3-carboxy-pyrazolone-(5).-. Do.

from l,3-diaminobenzene-6-sulphonic acid and 3,5-di- Example 264chloro-l,2-isothiazole-4-carboxylic acid chloride, after diazotizationat 40 C. at a pH of 7.5-6.5, with a solution of 40.5 parts of thedisodium salt of 2-sulphoacetylamino-5-hydroxynaphthalene-7-sulphonicacid, a reactive dyestuff of the formula In 700 parts of Water aredissolved neutral 58 parts of the dyestuff having the formula f -N=1 I-Nix-0H NEOsS- N3038- SOaH OH C1 N:N" NH HOBS\ NHCOCHrS0sH prepared bycoupling diazotized 1-hydroxy-2-amin0-4- chlorobenzene-S-sulphonic acidwith 2-methylamino-8- oGC-CG1 hydroxynaphthalene-6-su1phonic acid andcoppering the mp4) resultant azo dyestuff, and 21.6 parts of finelypowdered 3,5-dichl0ro-1,2-isothiazole-4-carboxylic acid chloride areadded and the mixture is stirred at 40-45 C., While continuouslyneutralizing the liberated hydrochloric acid to a pH of 5-6 with asodium carbonate solution, until free amino groups can no longer bedetected. The resultant reactive dyestulf of the formula is obtained,which dyes cellulose materials by the usual methods of application withthe use of sodium carbon- 0 C i u-O ate as acid-binding agent In fastorange shades.

Example 255 t Nfloas When the procedure described 1n Example 191 is followed, but instead of the aminoazo dyestuff there employed, 53.15 partsof the disodium salt of the aminoazo dyestuff obtained by couplingdiazotized 1-amino'4-nitrobenzene-2-sulph0nic acid with1-(2'-chloro-5-sulphois salted out, filtered ofi, washed and dried at40-50 C. phenyl)-3-methyl-pyrazolone-(5) and subsequent redu0 Thedyestuif dyes cellulose materials by one of the methtion of the nitrogroup with sodium sulphide, are acylated ods described above, in veryfast violet shades,

with 3,5-dichloro-1,2-isothiazole-4-carboxylic acid chlo- Dyestutf ofsimilar properties are obtained in a manner ride, a valuable reactivedyestuff is likewise obtained, with analogous to the method describedabove from the copwhich cellulose materials can be dyed or printed bythe per complexes, obtained by simple de-methylating or oxiusual dyeingand printing processes in fast yellow shades. dizing coppering, of themonoand diazo dyestuffs pro- Similar reactive dyestuffs are obtained byacylating induced from the diazo and azo components listed in the steadof the aminoazo, dyestuff mentioned above, an following table:

Ex. Coupling No. Diazo component Azo component pH Shade 265--..l-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid.2-an1ino-8-hydroxynaphthalene-3,ddisulphonic acid Reddish-Violet. 266 dol-amino-S-hydroxynaphthalene-3,6-disulphonic acid 10 Bluish-violet.267.... 2-amino-naphthalene-4,6,8-trisulphonic acid (coppered2-l1ydroxy-Sacetylaminonaphthalene t-sulphonic acid 8-9 Reddish-blue.

with oxidation). (saponified). 268.... I-amidnQ-ZAI;ydro-6-nitronaphthalene-4-sulphonic acidl-hydroxy-&ethoxynaphthalene-3,6-disulphonic acib 10 Blue.

(re uce 269.-.. l-hydroxy-2-aminobenzene4,6-disulphonic acid2-hydroxy-S-aminonaphthalone-5,7-disulphonic acid 10 Rob. 270.-..2-amino-naphthalene-4,8-disulphonic acid (coppered o 89 Blue.

with oxidation). 271--.. 2-amigonaphthagene-4,6,8-trisulphonic acid(coppered 2-hydroxy-3-aminonaphthalene-7-sulphonic acid 8-9 Do.

wit oxidation 272--.. 3-111ethoxy-4-amino-(S-methylazobenzene-2,4-disul-2-1nethylarnino-5-hydroxynaphthalene-7-sulph0nic acid.. 10 Navy Blue.

phonic acid (coppered with demethylation). 273 do2-amino-8-hybr0xynapl1thalene-3,6-disulphonic acid- 10 Do. 274-. S-Inethoxy-4-amino-6-mcth ylazobenzene-2,4'-di- 2-amino-5-h ybroxynaphthalone-1,7-disulphonic acid 10 sulphonic acid (coppered withdemethylation) D0. 275--.- 3-methoxy-4-amino-6-methylazobenzene-2,5-di-Z-methylamino-dhydroxynaphthalene-7-sulphonic acid.- 10 Do.

sulphonic acid (coppered with demethylation). 276 .do2-arnino-8-hydroxynaphthalane-3,6-disulphonic acid. 10 Do. 277 ..do2-a1nin0-5hydroxynaphthalene-l,7-disulphonic acid. 10 Do.

Example 278 By proceeding according to the instructions of Example 224,but using instead of the 54.7 parts of the disodium salt of1-amino-4-[(2'-methyl-3-aminophenyl)-amino]-anthraquinone-2,5-disulphonic acid there mentioned, 63.5 parts ofthe trisodium salt of 1-amino-4-[(3'- amin0phenyl)-amino]-anthraquinone2,4',6'- or -2,2',6'- trisulphonic acid, a reactive dyestuif is obtainedwhich dyes cellulose fibers by one of the usual dyeing methods in clearreddish-blue shades of very good fastness to wet processing.

By using equivalent amounts ofl-amino-4-(3'-aminophenyl-amino)-anthraquinone-2,5,8-trisulphonic acid,a valuable reactive dyestuif is likewise obtained which dyes cotton infast greyish-blue shades.

Example 279 In 300 parts of water are dissolved neutral 30.4 parts of2-amino-8-hydroxynaphthalene 3,6 disulphonic acid, heated to 45-50 C.,and 15. 6 parts of 3,5-dichloro-1,2- isothiazole-4-carboxylic acidchloride are added. 30 parts of a sodium carbonate solution are added inthe course of 5 hours so that the pH value is between 4 and 6. Theacylation product partially precipitates.

A freshly prepared diazonium salt solution from 13.6 parts ofp-arninobenzyl-sulphonic acid is added dropwise at 05 C. into asuspension of the acylation product, which has been mixed with 12.5parts of sodium carbonate. After subsequent stirring for 5 hours atice-bath temperature, the product is salted out with sodium chloride,filtered off with suction, washed with a dilute sodium chloride solutionand dried at 40 C. in a vacuum drier. The resultant dyestuif correspondsto the formula NaOaS By proceeding as stated above, but acylatinginstead of 30.4 parts of 2-amino-8-hydroxynaphthalene-3,6-disulphonicacid, 30.4 parts of 2-amino-5-hydroxynaphthalene-1,7disulphonic acidwith 3,5-dichloro-1,2-isothiazole- 4-carboxylic acid chloride andcoupling the coupling component containing the reactive groups withdiazotized p-aminobenzyl-sulphonic acid, a readily soluble reactivedyestuif is obtained which dyes fabrics containing cellulose fibers inbrilliant reddish-orange shades.

A cotton or cellulose fabric is impregnated on the foulard at 25 C. witha solution containing per liter of liquor, 30 g. of the dyestulfdescribed in paragraph 1 of the present example, 100 g. of urea and 20'g. of sodium carbonate, squeezed off to a moisture content of about 100%and the moist fabric is again rolled up. After standing at roomtemperature for 24 hours, the fabric is rinsed, boiled with soap in theusual manner, and

dried. A brilliant scarlet dyeing of good fastness to wet processing andlight is obtained.

A cotton or cellulose fabric is impregnated on the foulard at 20-25 C.with a solution containing per liter of liquor, 30 g. of the dyestuifdescribed in paragraph 1 of the present example, g. of urea and 20 g. ofsodium carbonate, squeezed off to a moisture content of about 100% andsteamed at 103 C. for 10 seconds. After rinsing, boiling with soap, anddrying, a brilliant scarlet dyeing of good fastness to wet processingand light in likewise obtained.

A cotton fabric is impregnated with a solution at 20-25 C., whichcontains per liter of liquor, 20 g. of the dyestuff obtainable accordingto paragraph 1 of the present example and 0.5 g. of a non-ionic wettingagent (for example, a polyethoxylated oleyl alcohol) as well as 150 g.of urea and 15 g. of sodium bicarbonate. The fabric is subsequentlysqueezed off between two rubber rollers to a moisture content of about100%. After an intermediate drying at 5060 C., the fabric is heated atC. for 10 minutes and the dyeing thus obtained is thoroughly rinsed withhot water and treated at the boil for 10 minutes with a solutioncontaining per liter, 5 g. of Marseilles soap and 2 g. of sodiumcarbonate. After rinsing and drying, an intense scarlet dyeing of goodfastness to wet processing and light is obtained.

When a cellulose fabric is printed with a printing paste which contains,per kilogram, 30 g. of the dyestuif described in paragraph 1 of thepresent example, 100 g. of urea, 300 g. of water, 500 g. of alginatethickening (60 g. of sodium alginate per kilogram of thickening), 10 g.of sodium carbonate and 10 g. of the sodium salt of3-nitr'obenzene-sulphonic acid and which is made up with Water to 1 kg.,the material is subsequently subjected to an intermediate drying andthen steamed in a suitable steaming apparatus at 103-115 C. for 30 seconds, followed by rinsing and boiling with soap, an intense scarletdyeing of good fastness properties is obtained.

100 parts of wool are introduced at 40 C. into a bath which contains, in5000 parts of water, 1.5 parts of the dyestuff described in paragraph 1of the present example as well as 6 parts of 30% acetic acid and 0.5part of a polyethoxylated stearylamine derivative containing hydroxylgroups. The dyebath is brought to the boil within 30 minutes, and dyeingis then carried out at boiling temperature for one hour. After rinsingand drying, a brilliant scarlet dyeing of good fastness to washing,milling, and light is obtained.

Example 280 2-amino-1-methylbenzene-3,5-disulphonic acid (monosodiumsalt), 28.9 parts, is diazotized and the diazo compound is coupled with13.7 g. of 1-amino-2-methoxy-5- methylbenzene in a weakly acidic medium.The resultant monoazo dyestulf is isolated and subsequently diazotized,or also immediately diazotized in solution without isolation, andcoupled in an alkaline medium with 25.3 parts of 2 methylamino--hydroxynaphthalene-7-sulphonic acid. The diazo dyestuffs obtainedis salted out by the addi tion of sodium chloride, filtered off withsuction, and the isolatedproduct is metallized with about 50 parts ofcrystalline copper sulphate, 40 parts of diethanolamine and 50 parts ofammonia (d. 0.88) at 95-100 C. within about 5 hours. The dyestuff isisolated from the coppering solution by the addition of salt and carefulacidification.

The coppcred amino-diazo dyestuff is then acylated in an aqueoussolution at a pH of 4-6 and at a temperature of 45 C. with 21.5 parts of3,5-dichloro-1,2-isothiazole- 4-carboxylic acid chloride, whilemaintaining the pH value within the stated range by the addition ofsodium carbonate. When the acylation is completed, the dyestuff isisolated with sodium chloride and dried at 50 C. In the form of the freesulphonic acid, the dyestuff corresponds to the formula It dyescellulosefabrics by the processes known for reactive dyestuffs in navy blueshades fast to wet processing and light.

Further dyestuffs according to the invention can be produced in asimilar manner, when the above-mentioned monoazo dyestuff from2-amino-1-methylbenzene-3,5 -disulphonic acid and l-amino2-methoxy-5-methylbenzene is combined with the amino-naphthol-sulphonicacids given below and with 3,5-dichloro-1,2 isothiazole-4-carboxylicacid chloride in giverrabovex- Couplingcomponent:

Z-arnino-5-hydroxynaphthalene-1,7-disulphonic acidZ-amino-8-hydroxynaphthalene-3,6 disulphonic acid The resultantdyestuffs have a blue color.

Example 281 4 ureido-2-amino-1-hydroxybenzene-S-sulphonic acid, 0.1 mol,is diazotized and coupled in a soda-alkaline medium with 0.1 mol of1-amino-8-hydroxynaphthalene-2,4- disulphonic acid. The couplingsolution is adjusted with caustic soda to a content of 2 mol/liter andthen boiled under reflux for 3 hours to saponify the ureido group. Aftercooling, the mixture is neutralized with hydrochloric acid. The dyestuffis metallized by the addition of parts of copper sulphate and 100 partsof a 2 N sodium hydroxide solution at.45." C., and a pH value of 4-6,and acylated after minutes at a pH value of 4-6 and at a temperature of-60 C. with 0.1 mol of 3,5- dichloro-1 ,2-isothiagoleA-carboxylic acidchloride. The resultant dyestuff of the formula is salted out. A bluedyeing is obtained on cotton.

' Example'282 accordance with the instructions initially at 0-3 C.,finally at 2035 C., with the addition of 300 ml. (295 g.) of pyridine,and the pyridine is then distilled off from the resultant solution ofcopper-phthalocyanine-disulphonic acid-monosulphonic acid-(3'-sulpho-4'-methyl-arninomethyl-anilide) at a pH of 9.0 with steam. 280 grams offinely powdered 3,5-dichloro-1,2- isothiazole-4-carboxylic acid chlorideare added in portions in the course of 4-6 hours to the solution whichhas been cooled to 30 C., while maintaining a pH of 7.5-9.5 by theaddition of a dilute sodium hydroxide solution. At the same time thereaction mixture is diluted with water as required, so that the dyestuffalways remains dissolved.

A dyesuff solution of 10 liters is obtained which is se arated from theexcess acylating agent, adjusted to a pH of 7.0 by the addition ofacetic acid and the dyestuff is precipitated by adding 2.5 liters of aconcentrated sodium chloride solution while stirring.

After filtering off with suction and drying at C., a

clear turquoise-blue dyestuff is obtained, which is fixed on cotton froma soda-alkaline solution at 70-90 C. with a very good yield and verygood fastnc-ss to washing.

By using the NiPc-3,3,3"-trisulphonic acid chloride as startingmaterial, a turquoise-blue shade of equally valuable properties isobtained, Which is only slightly more greenish.

Example 283 In parts by volume of concentrated hydrochloric acid aredissolved 12.5 parts of 3-amino-4-sulphobenzyl- N-methylamine and 4parts of sodium nitrite in 20 parts by volume of water are addeddropwise to the solution. The resultant clear diazonium salt solution isadded dropwise at 30-35" C. to an aqueous solution of the equimolaramount of 1-N-benzoyl-amino-8-hydroxynaphthalene-4,6-disulphonic acidand 16 parts of sodium bicarbonate in 200 parts by volume of Water.

The dyestuff partially precipitates and is redissolved by the additionof 2000 parts by volume of water. 15 parts of3,5-dichl0ro-1,2-isothiaZole-4-carboxylic acid chloride are then addedat 4050 C. The pH is kept between 7 and 8 by the drop-wise addition of asodium carbonate solution. When the acylation is completed, as can berecognized from the consumption of sodium carbonate, the dyestuff isseparated with 10% of sodium chloride, filtered off with suction,pressed off and dried in a vacuum drier at 40 C. The bluish-red dyestuffobtained corresponds, in the form of the free acid, to the formula Thedyestuff obtained from 6-nitro-2-diazo-l-hydroxybenzene-4-sulphonic acidand Z-hydroxynaphthalene by soda-alkaline coupling, 38.9 parts, isstirred at a pH of 8 in 200 parts of water at a temperature of 7080 C.67.9 parts of the chromium complex compound of the azo dyestuff from4-chloro-2diazo 1 hydroxybenzene-6- sulphonic acid and1-amino-8hydroxy-naphthalene-3,6- disulphonic acid containing l-chromiumatom per dyestuff molecule are introduced into this suspension, whilemaintaining a pH between 7 and 9 by the dropwise addition of a sodiumcarbonate solution. After 20 minutes at 70-80 C., a dark blue solutionhas formed. The paper chromatogram shows that a homogeneous mixedcomplex has formed. The mixed complex is acylated within 30 minutes at45 C. and a pH of 4-6 with 21.6 parts of3,5-dichloro-1,2-isothiazole-4-carboxylic acid chloride, the pH beingkept Within the stated range by the dropwise addition of a sodiumcarbonate solution. The acylated dyestufl is salted out with 20% ofpotassium chloride, filtered off and dried at 50 C. A dark powder isobtained which dissolves in water, with a blue-grey color.

In the form of the pentasodium salt, the dyestuif corresponds to theformula Valuable dyestuifs can also be obtained in the manner describedin the present example from the starting components listed in thefollowing table. For the production of these dyestuffs, the azo dyestuifwhich contains the reactive group in the 2:1 mixed complex is alwaysused as 1:1 chromium complex.

tion is adjusted to a pH of -8 and 2.2 g. of 3,5-dichloro-1,2-isothiazole-4-carboxylic acid chloride are introduced in smallportions at 45 C. At the same time, a dilute sodium hydroxide solutionis added dropwise in such a manner that a pH of 7.5-8.5 is maintainedduring the reaction. The mixture is further stirred at 40-45" C. untilthe starting material has completely disappeared, filtered off withsuction from excess isothiazole-carboxylic acid chloride and salted at40 C. with a sufficient amount of solid sodium chloride to obtain anapproximately 10% sodium chloride solution. The product is filtered offwith suction, washed with a little sodium chloride solution and theresultant dyestuif of the formula NaOaS O IIIH;

is dried below 40 C. in a vacuum. About 8.5 g. of the dyestulf areobtained in the form of blue-green needles.

The dyestutf dyes cotton by the methods customary for reactive dyestuifsin intense blue-green shades of good fastness to wet processing andlight.

The 1-amino-4 (4' aminophenyl amino) anthraquinone-2,5,8-trisulph0nicacid used as starting material is obtained as follows: 31.2 g. ofp-phcnylene-diamine are introduced under nitrogen into a solution of 62g. of l-amino-4-bromo-anthraquinone-2,5,8 trisulphonic acid sodium saltand 12 g. of sodium carbonate and stirred with the addition of a CuClpaste at 40 C., until disulphonated bromoaminoacid is no longerindicated. The

1:1 Chronium complex (listed in terms of reaction components) Ex. No.

285--- 4-nitro-2-amino-1-hydroxybenzene-fi-sulphonic acid 1-amino-S-hydroxynaphthalene-3,6disulphonic acid.

Metal-free dyestufl (listed in terms of coupling components) Shade oncotton do Do. do D0. 288 do 4-n1tr0-2-am1no-l-hydr0xybenzene2-hydroxy-naphthalene-(i Do.

sulphonic acid. 289 ..do .do Do. 290 .-do4-nitr0-2-arnino-1-hydroxybenzene 1-hydroxy-naphthalenei- Navy blue.

sulphonic acid. 291 ..do6-nitro-2-amino-1-hydroxybenzene-4-sulphonic-acid 2-hydroxy Black.

hybroxy-naphthalene. 292 d0 4-nitro-2-amin0-1-hydroxybenzenel-acetylamino-7-hydroxy- Do.

naphthalene. 293 .-do 6-nitro-1-amino-2-hydroxynaphthalene-i-sulphonicacid- 2- Do.

hydroxynaphthalene. 294--" 4-nitro-2-amino-1-hydroxybenzene-dsulphcnieacid- 1- 4-nitro-2-amino-1-hydroxynaphthalene-6-sulphonic acid 2- Do.

amino-B-hydroxynaphthaleue-4,6-disulphonic acid. hydroxynaphthalene.295--.. 4-chloro-2-amino-1-hydroxybenzene-G-sulphonic acid- 1-4-nitro-2-amino-l-hydroxybezene 2-hydroxynaphthalene Blue-black.

amino-8-hydroxynaphthalene-3,6disulphonic acid. 296 do do Do. 297 do4-nitro-2-amino-1-hydroxybenzenefiz-hydroxynaphthalene-G- Do.

sulphonic acid. 298 .do 4-chloro-2-amino-1-hydroxybenzene2-hydroxynaphthalene-- Navy blue. 299 do 4mitro-2-amino-1-hydroxybenzene1-acetylamino-8-hydroxy- Blue.

naphthalene-3,6-disu1phonic acid. 300 do4-nitr0-2-amino-1-hydroxybenzeue-d-amino-S-hydroxy- Navy blue.

naphthalene-2,4-disulphonic acid. 301 do6-nitro-1-amino-2-hydroxynaphthalene4-sulphonic acid- 2- Blue-black.

hydroxynaphthaiene. 302 d0 2-aminobenzene-l-carboxylie acid-5-sulphonieacid- 1-phenyl- Grey-green.

3-Inethy1-5 pyrazolone. 303 4-nitro-Z-aminoJ-hydroxybenzene-fi-sulphonicacid 1- fi-nitro l-amino-z-hydroxynaphthalene-i-sulphonic acid- 2-Black.

amino-8-hydroxynaphthalene-3,6Fdisulphonie acid. hydroxynaphthalene.304" 4-ehloro-2-aminoJ-hydroxybenzene-6-su1phonic acid1-4-chloro-2-amino-1-hydroxybenzene l-(4'-sulphophenyl)-3- Violet.

amino-B-hydroxynaphthalene-3,6-disulphonic acid. methyl-apyrazolone.305--.. 4-methyl-2-amino'l-hydroxybenzene-fi-sulphonic aeid 1-4-chloro-2-amino-l-hydroxybenzene 2-hydroxynaphthalene- Reddish-blue.

aminoEi-hydroxynaphthalene3,6disulphonic acid. 6-sulphonic acid. 3064-nitro-2-amino-1hydroxybeuzene-fi-sulphonic aeid-1-5-nitro-2-an1ino-1-hydr0xybenzene 2-hydroxynaphthalene-ti Black.

amino-8mydroxynaphtha1ene-3,6 disulphonic acid. sulphonic acid. 307 d04-nitro-2-amin0 1-hydr0xybenzene 2-hydroxynaphthaleue-8- Do.

sulphonic acid. 308 do-nitro-Z-amino-l-hydroxybenzene-d-hydroxynaphthalene-5= Do.

sulphonic acid. 309 ..do 6-nitro-4-chloro-1-hydroxybenzene-1-hydroxynaphthalene-fi- Do sulphonic acid.

solution is then mixed with dilute hydrochloric acid, the precipitateddyestuff is filtered off with suction, washed with dilute hydrochloricacid, treated in 300 ml. of water with sufiicient dilute sodiumhydroxide solution that it just dissolves and that the dyestuffprecipitates in the hot in the form of the sodium salt; the product isthen Washed and dried.

Example 311 34 A blue-black print of excellent fastness to light andwashing is obtained on cotton by the known processes.

In the examples, those dyestuffs illustrated by formulae, which containsulphonic acid groups, are generally given in the form of the sodiumsalts of the sulphonic The trisodium salt of the dyestuff obtained bysodaalkaline coupling from diazotized 4-chloro-2-amino-lacldsg Q E f thei aclds (SO3H) or other salts hydroxybenzene-6-sulphonic acid andl-amino 8 hyg 9 m a flown manner droxynaphthalene-3,-disulphonic acid,62 parts, is mixed 1 g if f th f r 1 in 300 parts of water at 70-80 C.and at a pH of 8-9 ye u 0 e o mu with 54.2 parts of the 1:1 chromiumcomplex of the 10 dyestuff from 6-nitro-1diazo-2 hydroxynaphthalene 4-sulphonic acid and 2-hydroxynaphthalene. A deep blue 1 solution isformed after 10 minutes. m H

The mixed complex is acylated within about minutes at 45 0. and a pH of4-6 with 21.6 parts of 3,5-di- 15 s mchloro-1,Z-isothiazole-4-carboxylic acid chloride. The pH value is keptconstant by the dropwise addition of a sodium carbonate solution. Theacylated dyestufi is sepawherein F stands f0 r a Water-soluble dyestutfselected Zi 2 2 f gg g s fi fiteredlofi Wlth from the group consistingof nickel phthalocyanine and Ion an me a an as 6 0mm a copperphthalocyanine dyestuffs; W is a bridge member OzN 9 joined to anaromatic nuclear carbon atom of F and selected from the class consistingof:

"N=N -NH(OH2).. and -I\IT(CHQ),.

t t R 0 NHC0O--CC1 O 1 wherem the N atom 1s connected with the COgrouping; O s R is lower alkyl or lower alkyl substituted by OH; and 3 sn is 0 or 1; X and Y are selected from the class consistso ing ofchlorine and bromine; and m is a number ranging from 1 to 2. C1 2. Adyestuff of claim 1 wherein W is --NR- and R Guhthaloc anine is hydrogenor methyl.

3. The dyestutf of claim 1 having the formula References Cited UNITEDSTATES PATENTS 2,396,145 3/1946 Anders et a1. 260-158 XR 3,299,0841/1967 Simonnet et a1. 260--303 FOREIGN PATENTS 417,980 10/1934 GreatBritain. 236,708 6/ 1945 Switzerland. 341,247 11/ 1959 Switzerland.

FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

P0405) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3r48o'64l Dated November 1 9 Inventoflg) Karl-Heinz Schundehutte, et al.Page 1 It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

I" y I Column Line Error 1 l0 "appilcation" should read application 1 44"of" should read or l 48 "azo" should read aza 3 34 "collars" shouldread rollers 6 formula a bond from "NaO S" to the structure is missing 7Example 14 "lamino:2-" should read l-amino-Z- under Diazo componentheading 7 Example 22 "ClC-- C" should read formula N c PO-IOED PatentNo.

Inventor(s) It is certified Dated November 25, 1969 Karl-HeinzSchundehutte et al. Page 2 that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

{- Column Line Example 17 under Coupling component heading Example 21under Coupling component heading Example 28 under Coupling componentheading Example 30 under Coupling component heading Example 32 underCoupling component heading "2-amino:S-hydroxy" should read2-amino-5-hydroxy "l(3'-,5'-dichloro-" should read 1-(3 ,5'dichloro-"3-methylpyrazolene-5" should read 3-methylpyrazolone-S we"disulpho-naphtyhl-" should read disulpho-naphthyl- P0405) UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION patent 3,480,641 Dated November25, 1969 Inventor) Karl-Heinz Schundehutte, et al. Page 3 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column Line Error 8 Example 34 "acetalymino" should read underacetylamino Coupling component heading 8 Example 35 "NaC S" should readNaO S second formula 9 Example 43 "4,6.disulphonic" should read Amino4,6-disulphonic dyestuff heading 9 24 "tretra-" should read tetra- 9 4O"isoethiazole" should read isothiazole 9 Example 49 "C' C" should readformula ClC N

